CN102143983B - Hydrophilic polyurethane dispersions based on TCD - Google Patents

Abstract

The present invention relates to novel aqueous polyurethane dispersions which can be used for producing hydrophilic coatings.

Description

Hydrophilic polyurethane dispersion based on TCD

The present invention relates to can be used for make the aqueous polyurethane dispersion of the innovation of hydrophilic coating.

Hydrophilic surface is arranged on medical devices for example can be so that their application greatly improves on the conduit.By the hydrophilic surface adsorbed film of water that contacts with blood or urine, the insertion of feasible urine or vessel catheter and mobile easier.Reduced the friction between catheter surface and the wall of container thus, and the therefore easier insertion of conduit and movement.Also can before insertion, carry out the directly wet water of device, reduce friction with the formation by even moisture film.Relevant patient stands less pain and has reduced risk to the tube wall injury by these measures.In addition, when conduit is used for contact with blood, the risk of formation blood clotting is arranged usually.In this respect, hydrophilic coating is believed to be helpful in the anticoagulant coating usually.

What be suitable in principle making respective surfaces is by the solution of corresponding urethane or the polyurethane coating of the initial preparation of dispersion.

For example, US 5,589, and 563 have described end group with surface modification to the application of the polymkeric substance that is used for biomedical sector, and these coating also can be used for applying medical devices.The coating of gained is by solution or the initial preparation of dispersion, and polymer coating comprises the different end group of the polyethylene oxide that is selected from amine, fluorinated alkanol, polydimethylsiloxane and amine end-blocking.Yet as the coating that is used for medical devices, these polymkeric substance do not have satisfied performance, particularly with regard to required wetting ability.

DE 199 14 882 A1 relate to urethane, polyurethane-urea and the polyureas of the form of dispersing or dissolving, and it synthesizes (ausbauen) by following component:

A) at least a polyol component,

B) at least a two, three and/or polyisocyanate component,

C) at least a wetting ability nonionic composed of the following components or the synthetic component of latent property ion: have the compound that at least one is reactive group and has at least one Hydrophilicrto polyether chain isocyanate groups, and/or have at least one and can form salt and optional at least part of and the group of form and have at least one is reactive group to isocyanate groups compound

D) at least a being different from a)-c) and have synthetic component that at least one molecular weight ranges that isocyanate groups is reactive group is 32-500 and

E) at least a simple function end-capping reagent.The polymeric dispersions that therefore must have the simple function end-capping reagent is used for sizing material.

DE 199 14 885 A1 relate to the dispersion based on urethane, polyurethane-polyurea and polyureas, and it is preferably the reaction product of following component:

A) at least a polyol component,

B) at least a two, three and/or polyisocyanate component,

C) the optional at least a synthetic component of (property of diving) ion that is grouped into by following one-tenth: have at least one and the NCO group is reactive group and has at least one and can form salt and optional at least part of and the compound of the group of form,

D) the synthetic component of Ren Xuan at least a nonionic wetting ability, it is made up of simple function to four sense with regard to the isocyanic ester addition reaction and the compound that contains at least one Hydrophilicrto polyether chain,

E) Ren Xuan at least a being different from a)-d) and have synthetic component that the molecular weight ranges that isocyanate groups is reactive group is 32-500 and

F) at least a simple function end-capping reagent of 0.1-15 weight %, wherein at least 50% is made up of dimethyl pyrazole,

A)-f) summation is 100%, and c wherein) or d) can not and use so that form the amount of stabilising dispersions for 0.This dispersion is particularly useful for applying mineral substrates, to japanning and the sealing of timber and wood materials, and to japanning and the coating of metallic surface, the japanning of plastics and coating, and the coating of fabric and leather.

These are not used in medical purpose by the known polyurethane-urea dispersion of prior art, namely are used for applying medical devices.In addition, hitherto known polyurethane-urea coating has defective usually: they are not for enough hydrophilic for the coatings applications of medical device.

In this respect, US 5,589, and 563 have recommended the end group of surface modification for the biomedical polymkeric substance that can be used for applying medical devices.These polymkeric substance comprise the different end group of the polyethylene oxide that is selected from amine, fluorinated alkanol, polydimethylsiloxane and amine end-blocking.Yet as the coating that is used for medical devices, these polymkeric substance do not have satisfied performance equally, particularly with regard to required wetting ability.

Still undocumented European application No. 08153053.7 now known can be significantly for the manufacture of the aqueous dispersion of hydrophilic coating.

Have now found that, can further improve the mechanical property of these coating by using specific polycarbonate diol.

Therefore the present invention provides the polyurethane-urea that comprises polyurethane-urea dispersion, this polyurethane-urea

(1) by at least one based on the copolymer unit end-blocking of polyethylene oxide and poly(propylene oxide) and

(2) comprise the unit based on polycarbonate polyol of formula (I)

Formula (I).

According to the present invention, the composition that discovery is made up of these particular polyurethane ureas is suitable for the hydrophilic coating that is particularly useful for medical devices excellently, and they produce the smooth coating of excellence and reduce to form the risk of blood clotting simultaneously during treating with medical devices.

The polyurethane-urea that is used for the object of the invention is the polymerizable compound that has with lower unit:

A) repeating unit that comprises carbamate groups of at least two following formulas

With

B) at least one comprises the repeating unit of urea groups

。

According to of the present invention dispersion-based in the polyurethane-urea that does not have ion modification substantially.In the context of the present invention, it refers to that polyurethane-urea used according to the invention does not have ionic group substantially, does not for example particularly have sulfonate (Sulfonat), carboxylate salt (Carboxylat), phosphoric acid salt (Phosphat) and phosphonate (Phosphonat) group.

In the context of the present invention, term " does not have ion modification " and refers to ion modification substantially with 2.50 weight % at the most, preferred 2.00 weight % at the most, 1.50 weight % at the most especially, more preferably 1.00 weight % at the most, especially the share that is 0.50 weight % at the most exists, and does not most preferably have ion modification fully according to polyurethane-urea provided by the invention.

The polyurethane-urea of the above-mentioned type required in this invention is preferably the molecule of substantial linear, also can branching, although this is less preferred.In the context of the present invention, the substantial linear molecule is low initial cross-linking system, wherein based on the polycarbonate polyol component have preferred 1.7-2.3, more preferably 1.8-2.2, the very particularly preferably average hydroxy functionality of 1.9-2.1.This system still can fully be disperseed.

The number-average molecular weight of polyurethane-urea required in this invention is preferably 1000-200 000 g/mol, more preferably 5000-100 000 g/mol.This number-average molecular weight in N,N-DIMETHYLACETAMIDE 30 ℃ with respect to polystyrene as canonical measure.

Polyurethane-urea required in this invention by make comprise at least a polycarbonate polyol component a), at least a polyisocyanate component b), at least a polyoxy alkylidene ether amount of component b), at least a diamine and/or amino alcohol components d) and randomly, the synthetic component reaction of other polyol component and preparing.

Be dispersed in and obtain in the water according to dispersion of the present invention.

Therefore the present invention also provides a kind of method for preparing the polyurethane-urea dispersion, wherein make the polycarbonate polyol component a), at least a polyisocyanate component b), at least a polyoxy alkylidene ether amount of component b), at least a diamine and/or amino alcohol components d) and randomly, other polyol component reacts each other and disperses in water.

Component a) comprises at least a polycarbonate polyol a1), its by make carbonic acid derivatives for example the two functional alcohol reaction of diphenyl carbonate, methylcarbonate or phosgene and formula (II) obtain

Formula (II).

For in pressure reactor neutralization preparation at elevated temperatures, make TCD alcohol DM [3 (4), 8 (9)-two (methylol) three ring (5.2.1.0/2.6) decane/tristane dimethanol] and diphenyl carbonate, methylcarbonate or phosgene reaction.Preferably with dimethyl carbonate.Under the situation of using methylcarbonate, in the mixture with excess carbon dimethyl phthalate, remove degradation production methyl alcohol by distillation.

Measure by the OH value, based on these polycarbonate polyols a1 of the dibasic alcohol of formula (II)) have preferred 200-10 000 g/mol, more preferably a 300-8000 g/mol and the very particularly preferably molecular weight of 400-6000 g/mol.

Component a) is preferably above-mentioned polycarbonate polyol a1 based on the glycol of formula (II)) and other polycarbonate polyol a2) mixture.

The polycarbonate polyol a2 that these are other) preferably has 1.7-2.3, more preferably 1.8-2.2, the very particularly preferably average hydroxy functionality of 1.9-2.1.

In addition, measure by the OH value, polycarbonate polyol a2) has preferred 400-6000 g/mol, more preferably 500-5000 g/mol, be in particular the molecular weight of 600-3000 g/mol, it can for example pass through carbonic acid derivatives for example diphenyl carbonate, methylcarbonate or phosgene and polyvalent alcohol, and preferred diol reaction obtains.This suitable class dibasic alcohol comprises for example ethylene glycol, 1,2-and 1, ammediol, 1,3-and 1,4-butyleneglycol, 1,6-hexylene glycol, 1,8-ethohexadiol, neopentyl glycol, 1, the two hydroxymethyl hexanaphthenes of 4-, 2-methyl isophthalic acid, ammediol, 2,2,4-trimethylammonium penta-1, the 3-glycol, two, three or Tetraglycol 99, dipropylene glycol, polypropylene glycol, dibutylene glycol, polytetramethylene glycol, dihydroxyphenyl propane, tetrabromo-bisphenol and interior ester modified dibasic alcohol.

These polycarbonate polyols a2) comprises preferred 40-100 weight % hexylene glycol, preferred 1,6-hexylene glycol and/or hexane diol derivatives are as synthetic component, preferably except end OH base, have those of ether or ester group, example is by making 1mol hexylene glycol and 1mol at least, preferred 1-2mol caprolactone reaction or by making hexylene glycol and etherificate own obtain the product that two hexylene glycols or three hexylene glycols obtain.Also can use polyethers-polycarbonate diol.The hydroxyl polycarbonate should be substantial linear.Owing to introduce multifunctional component, especially low molecular weight polyols, they are branching slightly yet randomly.The example that is applicable to the polyvalent alcohol of this purpose comprises glycerine, 1,2,6-hexanetriol, 1,2,4-trihydroxybutane, TriMethylolPropane(TMP), tetramethylolmethane, quinite, N.F,USP MANNITOL, sorbyl alcohol, methylglycoside or 1,3,4,6-dianhydrohexitol.Be preferably based on 1,6-hexylene glycol and modification altogether-glycol for example 1, this class polycarbonate a2 of 4-butyleneglycol or 6-caprolactone).Preferred polycarbonate diol a2 in addition) is based on those of mixture of 1,6-hexylene glycol and 1,4-butyleneglycol.

In a preferred embodiment, in a), use polycarbonate polyol a1) with based on 1,6-hexylene glycol, 1, those polycarbonate polyols a2 of 4-butyleneglycol or its mixture) mixture.

At component a1) and mixture situation a2) under, based on the integral molar quantity of polycarbonate, a1) share that accounts for this mixture is preferably 5mol% at least, more preferably 10mol% at least.

Polyurethane-urea required in this invention has in addition derived from the synthetic components b of at least a conduct) the unit of polyisocyanates.

As polyisocyanates b), can be separately or with the mixture of any hope each other use those skilled in the art known and have 〉=1, all aromatics, araliphatic, aliphatic series and the alicyclic isocyanate of average N CO functionality preferably 〉=2, they prepare inessential by the method that phosgene method does not still contain phosgene.They also can have imino- Diazine diketone, isocyanuric acid ester, uretdione, carbamate, allophanate, biuret, urea,

The diazine triketone, Oxazolidone, acylurea and/or carbon imide structure.Polyisocyanates can be separately or is used with the mixture of any hope each other.

Preferred use is selected from has 3-30, the aliphatic series of the carbon backbone chain (not having the NCO group) of preferred 4-20 carbon atom or the isocyanic ester of alicyclic representative series.

Particularly preferred components b) compound is corresponding to the above-mentioned type of the NCO group with aliphatic series and/or alicyclic connection, two (isocyanato-alkyl) ethers for example, two and three (isocyanato-alkyl)-benzene,-toluene and-dimethylbenzene, the propane vulcabond, butane vulcabond, pentane vulcabond, hexane diisocyanate (hexamethylene diisocyanate for example, HDI), heptane vulcabond, octane vulcabond, the nonane vulcabond (for example is generally 2,4,4 and 2,2, trimethylammonium-the HDI of 4 mixture of isomers forms (TMDI)), nonane triisocyanate (for example 4-isocyanato-methyl isophthalic acid, 8-octane vulcabond), the decane vulcabond, the decane triisocyanate, the undecane vulcabond, undecane triisocyanate, dodecane vulcabond, the dodecane triisocyanate, two (isocyanato-methyl) hexanaphthene (H of 1,3-and 1,4- ₆XDI), 3-isocyanato-methyl-3,5,5-3-methyl cyclohexanol based isocyanate (isophorone diisocyanate, IPDI), two (4-isocyanato-cyclohexyl) methane (H ₁₂MDI) or two (isocyanato-methyl) norbornanes (NBDI).

Components b very particularly preferably) compound is hexamethylene diisocyanate (HDI), trimethylammonium-HDI (TMDI), 2-methylpentane-1,5-vulcabond (MPDI), isophorone diisocyanate (IPDI), 1, two (isocyanato-methyl) hexanaphthene (H of 3-and 1,4- ₆XDI), two (isocyanato-cyclohexyl) methane (H of two (isocyanato-methyl) norbornanes (NBDI), 3 (4)-isocyanato-methyl isophthalic acid-isocyanatomethyl (IMCI) and/or 4,4'- ₁₂MDI) or the mixture of these isocyanic ester.Other example is to have uretdione, isocyanuric acid ester, carbamate, allophanate, biuret, imino-

The diazine diketone and/or Diazine triketone structure and have derivative more than the above-mentioned vulcabond of two NCO groups.

In the preparation of polyurethane-urea required in this invention, components b) amount is preferably 1.0-3.5 mol, and more preferably 1.0-3.3 mol is in particular 1.0-3.0 mol, under each situation based on a) amount of compound of component.

Being used for polyurethane-urea of the present invention has derived from as synthetic amount of component b) polyethylene oxide and the unit of the multipolymer of poly(propylene oxide).These copolymer unit are present in the polyurethane-urea with the end group form and have particularly advantageous hydrophilic effect.

The non-ionic hydrophilized compound c of this class) for for example to have statistical average 5-70 by the per molecule that suitable starter molecules alkoxylate is obtained in a manner known way, the monobasic polyalkylene oxide Aethoxy Sklerol of preferred 7-55 ethylene oxide unit (Ullmanns Enzyklop die der technischen Chemie for example, the 4th edition, the 19th volume, Verlag Chemie, Weinheim, the 31-38 page or leaf).

Suitable starter molecules is saturated monohydroxy alcohol methyl alcohol for example for example, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, the amylalcohol of isomery, hexanol, octanol and nonyl alcohol, nonylcarbinol, n-dodecane alcohol, n-tetradecanol, cetyl alcohol, Octadecane alcohol, hexalin, the methyl-cyclohexanol of isomery or hydroxymethyl hexanaphthene, 3-ethyl-3-hydroxymethyl trimethylene oxide or tetrahydrofurfuryl carbinol, the diglycol monotertiary alkyl oxide is diethylene glycol monobutyl ether for example, unsaturated alcohol is vinyl carbinol for example, 1,1-dimethyl vinyl carbinol or oleyl alcohol, aromatic alcohol is phenol for example, the cresols of isomery or methoxyphenol, aromatic grease group alcohol is benzylalcohol for example, pmethoxybenzyl alcohol or styryl carbinol, secondary monoamine is dimethylamine for example, diethylamine, dipropyl amine, Diisopropylamine, dibutylamine, two (2-ethylhexyl) amine, the N-methyl-and N-ethyl cyclohexylamine or dicyclohexyl amine and heterocyclic secondary morpholine for example, tetramethyleneimine, piperidines or 1H pyrazoles.Preferred starter molecules is saturated monohydroxy alcohol.Especially preferably use diethylene glycol monobutyl ether as starter molecules.

Oxirane-oxyethane and propylene oxide can be used for alkoxylation with any order or with mixture.

The polyalkylene oxide Aethoxy Sklerol is the oxyethane that mixes and the polyalkylene oxide polyethers of propylene oxide, and preferred at least 30 mol% of their epoxy alkane unit, and more preferably at least 40 mol% are made up of ethylene oxide unit.Preferred non-ionic compound is to have 40mol% ethylene oxide unit and the polyalkylene oxide polyethers of the simple function mixing of 60mol% propylene oxide units at least at the most.

The molar average weight of polyoxy alkylidene ether is preferably 500 g/mol-5000 g/mol, and more preferably 1000 g/mol-4000 g/mol are in particular 1000-3000 g/mol.

In the preparation of polyurethane-urea required in this invention, amount of component b) amount is preferably 0.01-0.5 mol, and more preferably 0.02-0.4 mol is in particular 0.04-0.3 mol, under each situation based on a) amount of compound of component.

According to the present invention, can show that the polyurethane-urea that has based on the end group of the polyoxy alkylidene ether of the polyethylene oxide that mixes and poly(propylene oxide) is particularly suitable for preparing the coating with high-hydrophilic.

Polyurethane-urea required in this invention have derived from as synthetic component and serve as so-called chain extension agent d) at least a diamine or the unit of amino alcohol.

This class chain extension agent for example is diamine or polyamine and hydrazides, example is hydrazine, quadrol, 1,2-and 1, the 3-diaminopropanes, 1,4-diaminobutane, 1, isophorone diamine, 2,2, the isomer mixture of 4-and 2,4,4-trimethylhexamethylenediamine, the 2-methyl pentamethylene diamine, diethylenetriamine, 1,3-and 1, the 4-xylylene amine, α, α, α ', α '-tetramethyl--1,3-and-1,4-xylylene amine and 4,4 '-diamino-dicyclohexyl methane, the dimethyl ethylene diamine, hydrazine, adipic dihydrazide, 1, two (amino methyl) hexanaphthenes of 4-, 4,4'-diamino-3,3'-dimethyl dicyclohexyl methyl hydride and other (C ₁– C ₄)-two-and tetraalkyl--dicyclohexyl methyl hydride, for example 4,4'-diamino-3,5-diethyl-3', 5'-di-isopropyl dicyclohexyl methyl hydride.

The lower molecular weight diamine or the amino alcohol that contain active hydrogen that suitable diamine or amino alcohol are normally different to the reactive behavior of NCO group for example also have secondary amino group except primary amino, perhaps also have the compound of OH base except amino (uncle or secondary).The example of this compounds is primary and secondary amine, for example 3-amino-1-methylamino propane, 3-amino-1-ethylamino propane, 3-amino-1-cyclohexyl aminopropane, 3-amino-1-methylamino butane, and amino alcohol for example N-amino ethyl ethanolamine, thanomin, 3-aminopropanol, neopentyl alcohol amine, and preferred especially diethanolamine.

In their preparation, the component d of polyurethane-urea required in this invention) can be used as chain extension agent.

In the preparation of polyurethane-urea required in this invention, component d) amount is preferably 0.1-1.5 mol, and more preferably 0.2-1.3 mol is in particular 0.3-1.2 mol, under each situation based on a) amount of compound of component.

In another embodiment, polyurethane-urea required in this invention comprises the other unit that synthesizes the other polyvalent alcohol of component derived from least a conduct.

Other low molecular weight polyols e for the synthesis of polyurethane-urea) has the effect that makes polymer chain sclerosis and/or branching usually.Molecular weight is preferably 62-500 g/mol, and more preferably 62-400 g/mol is in particular 62-200 g/mol.

Suitable polyvalent alcohol can comprise aliphatic series, alicyclic or aromatic group.Here can mention that for example per molecule has the low molecular weight polyols of about 20 carbon atoms at the most, ethylene glycol for example, glycol ether, triglycol, 1, the 2-propylene glycol, 1, ammediol, 1, the 4-butyleneglycol, 1, the 3-butyleneglycol, cyclohexanediol, 1, the 4-cyclohexanedimethanol, 1, the 6-hexylene glycol, neopentyl glycol, hydroquinore dihydroxyethylether, dihydroxyphenyl propane (2, two (4-hydroxy phenyl) propane of 2-), Hydrogenated Bisphenol A (2, two (4-hydroxy-cyclohexyl) propane of 2-), and TriMethylolPropane(TMP), glycerine or tetramethylolmethane and its mixture, and under suitable situation, other low molecular weight polyols.Also can use esterdiol, for example two (beta-hydroxyethyl) esters of α-hydroxyl butyl-ε-hydroxycaproic ester, ω-hydroxyl hexyl-gamma-hydroxybutyric acid ester, hexanodioic acid-(beta-hydroxyethyl) ester or terephthalic acid.

In the preparation of polyurethane-urea required in this invention, if exist, component e) amount is preferably 0.05-1.0 mol, and more preferably 0.05-0.5 mol is in particular 0.1-0.5 mol, under each situation based on a) amount of compound of component.

Usually finish the components b that contains isocyanic ester) with hydroxyl or amine official can compound a), c), d) and the e that chooses wantonly) reaction, keep excessive with respect to the NCO slightly of reactive hydroxyl or amine compound simultaneously.These resistatess must decompose or seal so that not with big polymer chain reaction.This class reaction causes the three-dimensional cross-linked and gelation of batch of material, and therefore no longer may further process.

Yet routinely, during dispersion steps, make the hydrolysis of excess isocyanate group and decomposition by disperse water.

If with the isocyanic ester content sealing of remnants, then they also have the monomer f that is positioned at the end of the chain and makes their end-blockings under each situation during the preparation of polyurethane-urea required in this invention) as synthetic component.

These synthetic components on the one hand derived from the monofunctional compound of NCO radical reaction, monoamine for example, especially single secondary amine, or monohydroxy-alcohol.Here the example that can mention comprises the derivative of ethanol, propyl carbinol, ethylene glycol monobutyl ether, 2-Ethylhexyl Alcohol, 1-octanol, 1-dodecanol, 1-cetyl alcohol, methylamine, ethamine, propylamine, butylamine, octylame, lauryl amine, stearylamine, different nonyl oxygen base propylamine, dimethylamine, diethylamine, dipropyl amine, dibutylamine, N-methylamino propylamine, the amino propylamine of diethyl (methyl), morpholine, piperidines and its suitable replacement.

Because structural unit f) basic excessive for eliminating NCO in polyurethane urea solutions according to the present invention, therefore required amount depends on the amount that NCO is excessive substantially, and can not generally illustrate.

Save component f in a preferred embodiment of the invention), and therefore polyurethane-urea required in this invention only comprises component a)-d) and optional component e).

In the preparation of polyurethane-urea required in this invention, synthetic in greater detail component reaction as follows usually above making, make by component a), b), c) and optional e) react at first prepare the isocyanate-functional prepolymer that does not contain urea groups, wherein isocyanate groups and the isocyanic ester amount ratio that is reactive group is preferably 0.8-4.0, more preferably 0.9-3.8 is in particular 1.0-3.5.

In alternative embodiment, can also at first make a) independent and isocyanic ester b of component) reaction.Afterwards, can add amount of component b then) and e) and the reaction.Subsequently, usually before in being scattered in water, during or make afterwards that remaining isocyanate groups carries out amino-functional increase chain or end-blocking, be used for increasing the equivalence ratio that isocyanate-reactive group and the free isocyanate groups of prepolymer of the compound of chain roll into a ball and be preferably 40%-150%, more preferably 50%-120% is in particular 60%-120% (component d)).

In the present context, the preferably method preparation by so-called acetone method of polyurethane dispersions of the present invention.In order to prepare polyurethane dispersions by this acetone method, usually must not contain uncle or the component of secondary amino group a), c) and e), and for the preparation of the polyisocyanate component b of the polyurethane prepolymer of isocyanate-functional) all or part ofly introduce as initial charge, and randomly with can be miscible but isocyanate groups is the solvent cut of inertia with water, and will dilute or undiluted initial charge is heated to 50-120 ℃ temperature.Can accelerate the isocyanic ester addition reaction by using catalyzer known in the polyurethane chemistry, example is dibutyl tin laurate.Preferably synthesize without catalyzer.

Suitable solvent be conventional aliphatic ketone official can solvent for example acetone, butanone, it not only can be when the preparation beginning, and randomly also can be after a while by part adding.Preferred acetone and butanone.Other solvent for example dimethylbenzene, toluene, hexanaphthene, butylacetate, acetic acid methoxyl group propyl ester, solvent with ether unit or ester units can use equally, and can all or part ofly distill, and perhaps can all be retained in the dispersion.

Randomly, the amount of component b that begins also not have adding that will react subsequently) and e) be metered into.

Preferably do not add solvent and prepare prepolymer and in order to increase chain, just with suitable solvent, preferred acetone diluted.

The reactive moieties of prepolymer or fully but preferably carry out fully.Obtain to comprise the polyurethane prepolymer of free isocyanate groups group with body or solution in this mode.

Subsequently in further operation, if its also do not carry out or only part carry out, then use for example prepolymer that obtains of acetone or butanone dissolving of aliphatic ketone.

Subsequently, make possible NH ₂-, NH-official can and/or OH-official can component and residual isocyanate radical reaction.This increase chain/chain end-blocking can be before dispersion in solvent, during dispersion or in water, carrying out after the dispersion.Increased chain before preferably in being scattered in water.

Has NH ₂Group or NH group meet d) compound of definition is used for increasing under the situation of chain, preferably carries out the chain that increases of prepolymer before dispersion.

Increase the chain degree, in other words be used for increasing the equivalence ratio of the free NCO group of the NCO reactive group of compound of chain and prepolymer, be preferably 40%-150%, more preferably 50%-120% is in particular 60%-120 %.

Under suitable situation, amine component d) can be used for method of the present invention separately or with mixture with the form of water or solvent cut, any addition sequence is possible in principle.

If make water or organic solvent as thinner in the lump, then amount of diluent is preferably 70-95 weight %.

After increasing chain, carried out the preparation of polyurethane dispersions by prepolymer.For this purpose, under suitable situation, be accompanied by strong shearing for example the vigorous stirring polyether polyols with reduced unsaturation that will dissolve and increase chain introduce disperse water, perhaps be accompanied by stirring on the contrary disperse water added pre-polymer solution.The prepolymer that preferably water is added dissolving.

Usually the solvent that still is present in the dispersion is removed in distillation after dispersion steps then.Can during dispersion steps, remove equally.

The solid content of synthetic back polyurethane dispersions is 20-70 weight %, preferred 20-65 weight %.For The coating experiment, these dispersions of dilute with water are to allow to regulate changeably coat-thickness arbitrarily.All concentration of 1-60 weight % are possible; The concentration of preferred 1-40 weight % scope.

In the present context, can realize the layer thickness of any hope, for example the hundreds of nanometer is to the hundreds of micron, and higher and lower in the context of the present invention thickness also is possible.

Polyurethane-urea dispersion of the present invention can further comprise various conventional additives and components of striving the final application that realizes.

These a example is the additive (" medicament elution additive ") that pharmacological active substance, medicine and promotion pharmacological active substance discharge.

Can be used in the coating of the present invention on the medical devices and therefore may reside in according to the pharmacological active substance in the solution of the present invention and medicine for example is, antithrombotic agent, microbiotic, antitumor agent, tethelin, antiviral agent, anti-angiogenic agent, angiogenic agent, antimitotic agent, antiphlogistic drug, Cycle Regulation agent, gene, hormone, and their homologue, derivative, fragment, pharmaceutical salts and its combination.

The object lesson of this class pharmacological active substance and medicine therefore comprise antithrombotic (not forming thrombus) agent and other be used for suppressing acute thrombus disease, stricture of artery or late period restenosis reagent, example is heparin, streptokinase, urokinase, tissue-proplasmin-activation factor, antithrombotic alkane-B ₂Agent; Anti--the B-thromoboglobulin, prostaglandin(PG)-E, acetylsalicylic acid, Dipyridamole, antithrombotic alkane-A ₂Agent, mouse monoclonal antibody 7E3, three

Azoles pyrimidine, ciprostene, r-hirudin, ticlopidine, Nicoril etc.The same useful as drug of somatomedin is with fibromyosis under the inner membrance that suppresses the stricture of artery position, and perhaps any other cytostatic agent can be used for narrow location.

Pharmacological active substance or medicine also can be made up of vasodilator, with opposing vasospasm-for example spasmolytic such as Papaverine.Medicine can be for example calcium antagonist of vasoactive agent itself, perhaps α-and beta-adrenaline excitant or antagonist.Therapeutical agent can be for example cyanoacrylate or the scleroproein of medical science quality of biological adhesive in addition, and it for example is used for tissue valve prosthesis is bonded in coronary arterial wall.

In addition, therapeutical agent can be for example 5 FU 5 fluorouracil of antineoplastic agent, preferably has the control release vehicle (for example antineoplastic agent that uses ongoing control to discharge at knub position) for medicament.

Therapeutical agent can be microbiotic, preferably the control release vehicle combination that discharges from the coating of medical devices with the local infection center that is used in vivo.Similarly, therapeutical agent can comprise the purpose that steroid is used for the inflammation of inhibition local organization, perhaps is used for other reason.

The object lesson of suitable drug comprises following:

A) heparin, heparin sulfate, r-hirudin, hyaluronic acid, chondroitin sulfate, dermatan sulfate, keratan sulfate, solvating agent (lytische Mittel), comprise urokinase and streptokinase, their homologue, analogue, fragment, derivative and its pharmaceutical salts;

B) for example penicillin, cynnematin, vancomycin, aminoglycoside, quinolone, polymyxin, erythromycin of microbiotic; Tsiklomitsin, paraxin, clindamycin, lincomycin, sulphonamide, their homologue, analogue, derivative, pharmaceutical salts and its mixture;

C) taxol, how western taxol, immunosuppressor is sirolimus or everolimus for example, and alkylating reagent comprises mustargen, Chlorambucil, endoxan, melphalan and Yi Fu acid amides; Metabolic antagonist comprises methotrexate, Ismipur, 5 FU 5 fluorouracil and cytosine arabinoside; Plant alkaloid comprises vinealeucoblastine(VLB); Vincristine(VCR) and etoposide; Microbiotic comprises Zorubicin, daunorubicin, bleomycin and mitomycin; Nitrosourea comprises Carmustine and lomustine; Mineral ion comprises cis-platinum; Biological respinse properties-correcting agent comprises Interferon, rabbit; Angiostatin reagent and Endostatin reagent; Enzyme comprises asparaginase; And hormone, comprise tamoxifen and Drogenil, their homologue, analogue, fragment, derivative, pharmaceutical salts and its mixture;

D) for example Symmetrel, Rimantadine, ribavirin (Rabavirin), Kerecid, vidarabine, trifluridine, acycloguanosine, ganciclovir, zidovudine, phosphonoformate, Interferon, rabbit of antiviral agent, their homologue, analogue, fragment, derivative, pharmaceutical salts and its mixture; With

E) for example Ibuprofen BP/EP, dexamethasone or methylprednisolone of antiphlogistic drug.

Have the surface that suppresses to infect performance in order to produce, coating composition of the present invention can comprise infection known in the art and suppress activeconstituents.What their existence had promoted surface itself that make with coating composition of the present invention usually infects rejection significantly.

Use other additive for example antioxidant, pigment, treatment agent, dyestuff, matting agent, UV stablizer, photostabilizer, hydrophobizing agent, buffer substance, flow control auxiliary agent and/or be used for the thickening material of viscosity adjustment.

Polyurethane-urea dispersion of the present invention can be used for for example forming coating at medical devices.

Term " medicine equipment " is understood in the context of the present invention in a wide range.Suitable, the limiting examples of medicine equipment (comprising instrument) are contact lens (Kontaktlinse); Sleeve pipe; Conduit (Katheter), for example urology conduit such as catheter (Blasenkatheter) or ureteral catheter (Harnleiterkatheter); The central vein conduit; Ductus venosus or outlet or inlet conduits; Expanded balloon (Dilationsballon); Be used for angioplasty and bioptic conduit; Be used for introducing the conduit of support, embolism strainer or venacaval strainer; Balloon catheter or other inflatable medical apparatus; Endoscope; Laryngoscope; Tracheae device such as tracheae inner flexible tube, respiratory organ and other tracheae suction apparatus (Trachealabsaugger te); Bronchoalveolar lavage catheter; The conduit that in coronary angioplasty, uses; Guide rod inserts conductor etc.; Vascular plug; The pacemaker parts; Cochlear implant; The tooth that is used for feeding is implanted flexible pipe (Zahnimplantatschl uche f ü r die Nahrungszufuhr), drainage flexible pipe (Dr nageschl uche); And seal wire.

Dispersion of the present invention can for example be used for gloves, support and other implant in addition for the manufacture of supercoat; Outside (extracorporeal) blood flexible pipe (pipeline of delivery blood); Film for example is used for the film of dialysing; Blood filter; The apparatus that is used for auxiliary circulation; The bundle material that stretches tight that is used for wound care; Urinal and ostomy bag.Also comprise the implant that comprises the medicinal actives agent, for example be used for support or be used for balloon surface or be used for the medicinal actives agent of contraceptives.

Usually, described medicine equipment is formed by conduit, endoscope, laryngoscope, tracheae inner flexible tube, feeding tube, guide rod, support and other implant.

Coating particularly advantageous based on dispersion of the present invention is used for medical use, and this does not particularly contain organic solvent residues thing because of them, and therefore can not cause toxicity usually, and causes more significant wetting ability simultaneously, and this for example finds out from low contact angle.

Except improving the hydrophilicity of oilness, also be high blood compatibility level according to coating composition characteristics provided by the invention.This makes and is particularly advantageous for the blood contact with these coatings.Compare with prior art polymers, this material shows the trend of condensing of minimizing in the blood contact.

Outside medical technology, also imagined release of active agent and based on the system of hydrophilic coating material of the present invention, for example the solid support material as active substance is used for crop protection.Whole coating can be counted as active delivery systme and can for example be used for applying seed (seed-grain).Because the hydrophilicity of coating, the active substance that contains can manifest and show its desired result in wetting soil, ability that can the negative impact seed germination.Yet in drying regime, apply agent and make active substance adhere to seed reliably, therefore for example when seed is injected soil by seed broadcaster active substance can not separate; Because this separates, active substance may for example show unwanted effect (sterilant that should prevent the seed in the insect infestations soil by itself endangers honeybee) the fauna that exists.

Outside their application as the coating that is used for medical devices, use according to the other technology that polyurethane dispersions of the present invention also can be used in the non-medical field.

Therefore, polyurethane dispersions according to the present invention is for the preparation of protecting the surface to avoid the coating that hazes because of moisture, for the preparation of cleaning easily or self-cleaning surface.These hydrophilic coatings have also reduced the absorption of dirt and have prevented from forming water spots.Externally the application that can imagine in the field is for example window glass and dormer window, glazed facade or synthetic glass roof (Plexiglasd cher).In inner field, this class material can be used for applying the surface of health field.Application in addition is that ophthalmic lens or wrapping material for example are used for preventing that moisture from hazing or because the drop of water of condensation forms the coating of the food product pack of purpose.

Be applicable to also that according to polyurethane dispersions of the present invention the surface that arrangement contacts with water is used for reducing the purpose that infects.This effect also becomes anti-fouling effect.A very important application of this anti-fouling effect is the field of paint vehicle under water of wheel barnacle.Do not have the wheel barnacle of antifouling processing very rapidly to become and infected by marine organism, this causes therefore possible speed to reduce and higher fuel consumption by the friction that increases.Coating material of the present invention reduces or has prevented from being infected by marine organism, and prevents the above-mentioned defective that this infects.Other application in the antifouling paint field is for the goods of fishing for example all metal bases of fishnet and submersible service, for example pipeline, offshore drilling platform, sluice and sluice gate etc.Have the following shell of surface, especially water line that produces with coating of the present invention and also have the friction resistance that reduces, and the steamer of therefore ornamenting has the fuel consumption of minimizing or realized higher speed.This is particularly important in sport boat field and yacht construction.

Another key areas that is used for above-mentioned wetting ability coating material application is Printing industry.By means of coating of the present invention, can make hydrophobic surface hydrophilization and therefore available polarity printing-ink printing, perhaps can use the ink-jet technology printing.

Another field that is used for hydrophilic coating application of the present invention is the preparation for cosmetic applications.

Coating according to polyurethane dispersions of the present invention can apply by means of the whole bag of tricks.The example that is used for the suitable paint-on technique of these dispersions comprises that cutter is coated with, printing, transfer coating, spraying, spin coating or dip-coating.

Can apply the base material of broad variety, for example metal, fabric, pottery and plastics.Preferably apply by plastics or metal medical devices.The example of the metal that can mention comprises following: medical science stainless steel and Ni-Ti alloy.Having imagined can be by its many polymer materials of constructing medical devices, and example is polymeric amide; Polystyrene; Polycarbonate; Polyethers; Polyester; Polyvinyl acetate; Natural and synthetic rubber; Vinylbenzene and unsaturated compound be the segmented copolymer of ethene, butylene and isoprene for example; Polyethylene or polyethylene and polyacrylic multipolymer; Silicone; Polyvinyl chloride (PVC) and urethane.For hydrophilic polyurethane to the better sticking power of medical devices, before applying these wetting ability coating materials, can apply in addition suitable coating as substrate.

Embodiment

The NCO content of the resin of describing in embodiment and the comparative example passes through titrimetry according to DIN EN ISO 11909.

Solid content is measured according to DIN-EN ISO 3251.Use infrared drier to make polyurethane dispersions (1 g) be dried to constant weight (15-20 min) at 115 ℃.

Use derives from the mean particle size of high-performance particle sizer (HPPS 3.3) the measurement polyurethane dispersions of Malvern Instruments.

Tensile strength is measured according to DIN 53504.

Unless otherwise indicated, will be understood that weight % with the amount of % report and based on the aqueous dispersion that obtains.

Material and the abbreviation used:

Desmophen C2200: polycarbonate polyol, OH value 56 mg KOH/g, number-average molecular weight 2000 g/mol (Bayer MaterialScience AG, Leverkusen, DE)

Desmophen C1200: polycarbonate polyol, OH value 56 mg KOH/g, number-average molecular weight 2000 g/mol (Bayer MaterialScience AG, Leverkusen, DE)

Desmophen XP 2613 polycarbonate polyols, OH value 56 mg KOH/g, number-average molecular weight 2000 g/mol (Bayer MaterialScience AG, Leverkusen, DE)

Polyethers LB 25:(is based on the monofunctional polyethers of ethylene oxide/propylene oxide, number-average molecular weight 2250 g/mol, OH value 25 mg KOH/g (Bayer MaterialScience AG, Leverkusen, DE)

TCD alcohol DM derives from Celanese Chemicals, Dallas, 3 (4), 8 (9) of USA-two (methylol) three ring (5.2.1.0/2.6) decane/tristane dimethanols

Embodiment 1:

The preparation based on the alicyclic polycarbonate diol of TCD alcohol DM with 1300 g/mol number-average molecular weights

At 80 ℃ of pack in advance in the 16 l pressure reactors that top distillation annex, agitator and receptor are housed 5436 g TCD alcohol DM and 1.2 g acetyl acetone yttriums (III) and 3810 g methylcarbonates.Subsequently under nitrogen atmosphere, in 2h, will react batch of material and be heated to 135 ℃ and be accompanied by to stir and keep 24h, wherein pressure rises to 6.3 bar (absolute pressure).Make it be cooled to 60 ℃ and the feeding of permission air then.Remove degradation production methyl alcohol by distillation in having the mixture of methylcarbonate then, temperature progressively rises to 150 ℃.Again mixture was stirred 4 hours at 150 ℃ then, be heated to 180 ℃ subsequently, and then at 180 ℃ of restir 4h.Make then temperature be down to 90 ℃ and make nitrogen gas stream (5 l/h) by the reaction batch of material, during pressure be down to 20 millibars.After this in 4h, make temperature increase to 180 ℃ and maintenance 6h.In this operating period, in having the mixture of methylcarbonate, further remove methyl alcohol from the reaction batch of material.

After allowing air feeding and reaction batch of material to be cooled to room temperature, the faint yellow solid polycarbonate diol that obtains having following parameter:

M _n=1290 g/mol; OH value=87 mg KOH/g;

Embodiment 2:

The preparation based on the alicyclic polycarbonate diol of TCD alcohol DM with about 500 g/mol number-average molecular weights

As the program among the embodiment 1, use 7790 g TCD alcohol DM, 1.68 g acetyl acetone yttriums (III) and 3096 g methylcarbonates.

This obtains having the faint yellow polycarbonate diol of high viscosity of following parameter: M _n=496 g/mol; OH value=226 mg KOH/g; 75 ℃ viscosity=138 400 mPas.

Embodiment 3:

The preparation based on fat (ring) the adoption carbonic ether glycol of TCD alcohol DM and 1,4-butyleneglycol with about 1000 g/mol number-average molecular weights

As the program among the embodiment 1, use 5951 g TCD alcohol DM, 2732 g 1,4-butyleneglycol, 2.0 g acetyl acetone yttriums (III) and 6842 g methylcarbonates.

This obtains having the colourless polycarbonate diol of following parameter: M _n=943 g/mol; OH value=119 mg KOH/g; 75 ℃ viscosity=15 130 mPas.

Embodiment 4:(comparison)

Introduce 277.2 g Desmophen C, 2200,33.1 g polyethers LB 25 and 6.7 g neopentyl glycol in advance at 65 ℃, and by stirring 5 minutes.In 1 minute, at first add 71.3 g 4 at 65 ℃, two (isocyanato-cyclohexyl) methane (H of 4'- ₁₂MDI) and then add 11.9 g isophorone diisocyanates to this mixture.With mixture heating up to 110 ℃.After 16 hours, reach 2.4% theoretical nco value.Make the prepolymer that makes be dissolved in 711 g acetone at 50 ℃, and in 10 minutes, be metered into the solution of 4.8g quadrol in 16g water at 40 ℃ then.Follow-up churning time is 5 minutes.In 15 minutes, disperse by adding 590g water afterwards.By under reduced pressure distilling desolventizing.This obtains having the stable storing polyurethane dispersions of 40.7% solid content and 136nm mean particle size.

Embodiment 5: (invention)

65 ℃ of polycarbonate diol, 33.1 g polyethers LB 25 and 6.7 g neopentyl glycol of introducing 208.0 g Desmophen C, 2200,45.2 g embodiment 1 in advance, and by stirring 5 minutes.In 1 minute, at first add 71.3 g 4 at 65 ℃, two (isocyanato-cyclohexyl) methane (H of 4'- ₁₂MDI) and then add 11.9 g isophorone diisocyanates to this mixture.With mixture heating up to 110 ℃.After 16 hours, reach 2.6% theoretical nco value.Make the prepolymer that makes be dissolved in 700 g acetone at 50 ℃, and in 10 minutes, be metered into the solution of 4.8g quadrol in 16g water at 40 ℃ then.Follow-up churning time is 5 minutes.In 15 minutes, disperse by adding 550g water afterwards.By under reduced pressure distilling desolventizing.This obtains having the stable storing polyurethane dispersions of 39.0% solid content and 131nm mean particle size.

Embodiment 6:(invention)

65 ℃ of polycarbonate diol, 33.1 g polyethers LB 25 and 6.7 g neopentyl glycol of introducing 138.6 g Desmophen C, 2200,90.1 g embodiment 1 in advance, and by stirring 5 minutes.In 1 minute, at first add 71.3 g 4 at 65 ℃, two (isocyanato-cyclohexyl) methane (H of 4'- ₁₂MDI) and then add 11.9 g isophorone diisocyanates to this mixture.With mixture heating up to 110 ℃.After 2 hours 45 minutes, reach 2.8% theoretical nco value.Make the prepolymer that makes be dissolved in 700 g acetone at 50 ℃, and in 10 minutes, be metered into the solution of 4.8g quadrol in 16g water at 40 ℃ then.Follow-up churning time is 5 minutes.In 15 minutes, disperse by adding 550g water afterwards.By under reduced pressure distilling desolventizing.This obtains having the stable storing polyurethane dispersions of 39.6% solid content and 157nm mean particle size.

Embodiment 7:(invention)

65 ℃ of polycarbonate diol, 33.1 g polyethers LB 25 and 6.7 g neopentyl glycol of introducing 184.8 g Desmophen C, 2200,23.1 g embodiment 2 in advance, and by stirring 5 minutes.In 1 minute, at first add 71.3 g 4 at 65 ℃, two (isocyanato-cyclohexyl) methane (H of 4'- ₁₂MDI) and then add 11.9 g isophorone diisocyanates to this mixture.With mixture heating up to 110 ℃.After 21 hours, reach 2.9% theoretical nco value.Make the prepolymer that makes be dissolved in 650 g acetone at 50 ℃, and in 10 minutes, be metered into the solution of 4.8g quadrol in 16g water at 40 ℃ then.Follow-up churning time is 5 minutes.In 15 minutes, disperse by adding 490g water afterwards.By under reduced pressure distilling desolventizing.This obtains having the stable storing polyurethane dispersions of 40.3% solid content and 117nm mean particle size.

Embodiment 8:(invention)

65 ℃ of polycarbonate diol, 33.1 g polyethers LB 25 and 6.7 g neopentyl glycol of introducing 138.6 g Desmophen C, 2200,34.7 g embodiment 2 in advance, and by stirring 5 minutes.In 1 minute, at first add 71.3 g 4 at 65 ℃, two (isocyanato-cyclohexyl) methane (H of 4'- ₁₂MDI) and then add 11.9 g isophorone diisocyanates to this mixture.With mixture heating up to 110 ℃.After 18 hours, reach 3.3% theoretical nco value.Make the prepolymer that makes be dissolved in 650 g acetone at 50 ℃, and in 10 minutes, be metered into the solution of 4.8g quadrol in 16g water at 40 ℃ then.Follow-up churning time is 5 minutes.In 15 minutes, disperse by adding 450g water afterwards.By under reduced pressure distilling desolventizing.This obtains having the stable storing polyurethane dispersions of 40.5% solid content and 151nm mean particle size.

Embodiment 9:(invention)

65 ℃ of polycarbonate diol, 33.1 g polyethers LB 25 and 6.7 g neopentyl glycol of introducing 138.6 g Desmophen C, 2200,69.3 g embodiment 3 in advance, and by stirring 5 minutes.In 1 minute, at first add 71.3 g 4 at 65 ℃, two (isocyanato-cyclohexyl) methane (H of 4'- ₁₂MDI) and then add 11.9 g isophorone diisocyanates to this mixture.With mixture heating up to 110 ℃.After 2 hours 15 minutes, reach 2.9% theoretical nco value.Make the prepolymer that makes be dissolved in 650 g acetone at 50 ℃, and in 10 minutes, be metered into the solution of 4.8g quadrol in 16g water at 40 ℃ then.Follow-up churning time is 5 minutes.In 15 minutes, disperse by adding 520g water afterwards.By under reduced pressure distilling desolventizing.This obtains having the stable storing polyurethane dispersions of 38.0% solid content and 190nm mean particle size.

Embodiment 10:Comparative example 4 is with respect to contact angle and 100% modulus of embodiment of the invention 5-9

1. be used for the preparation of the coating of measurement static contact angle

By spin coater (RC5 Gyrset 5, Karl S ü ss, Garching, Germany) coating for the preparation of the measurement static contact angle on the slide glass that is of a size of 25 * 75 mm.For this purpose, slide glass is clipped on the sample disc of spin coater and with the moisture undiluted polyurethane dispersions of about 2.5-3g and evenly covers.Sample disc 1300 rev/mins down rotation obtained uniform coating in 20 seconds, be dried 15 min and then at 50 ℃ of dry 24h at 100 ℃.The coating slide glass that obtains is directly carried out contact angle to be measured.

Gained coating on slide glass is carried out static contact angle and is measured.Use derives from the video contact angle measurement device OCA20 with computer-controlled injection of Dataphysics, 10 Millipore water is put on sample, and measure their static wetting angle.Use antistatic drying machine to remove the static charge of sample surfaces (if existence) in advance.

2. be used for the preparation of the coating of measurement 100% modulus

Use 200 μ m scrapers prepared layer on separate-type paper, and make its dry 15 minutes at 100 ℃.Subsequently 100 ℃ of dryings 15 minutes.Molding according to DIN 53504 research punching out.

Use 200 μ m scrapers that coating is put on separate-type paper.Before membrane prepare, aqueous dispersion and 2 weight % thickening materials (Borchi Gel A LA, Borchers, Langenfeld, Germany) are mixed, and by stirring under RT 30 minutes.At 100 ℃ with dry 15 minutes of wet film.

Study according to DIN 53504.

3. result of study

Table 1: contact angle and 100% modulus of film that derives from the material of embodiment 4-9

The embodiment numbering	Contact angle (°)	100% modulus (N/mm 2)
			Comparative example 4	10	2.6
Embodiment 5	12	3.0
			Embodiment 6	17	6.7
Embodiment 7	16	3.6
			Embodiment 8	27	7.2
Embodiment 9	16	5.4

Compare with comparative example 4, the difference of embodiment of the invention 5-9 is that a part of polycarbonate diol Desmophen C2200 is replaced by polycarbonates glycol of the present invention.This material has those similar hydrophilicities with comparative example 4 as coating, and contact angle is always less than 30 °.100% modulus all is higher than comparative example 4.

Embodiment 11:(comparison)

Introduce 282.1 g Desmophen C, 2200,22.0 g polyethers LB 25 and 6.7 g neopentyl glycol in advance at 65 ℃, and by stirring 5 minutes.In 1 minute, at first add 71.3 g 4 at 65 ℃, two (isocyanato-cyclohexyl) methane (H of 4'- ₁₂MDI) and then add 11.9 g isophorone diisocyanates to this mixture.With mixture heating up to 110 ℃.21.5 after hour, reach 2.4% theoretical nco value.Make the prepolymer that makes be dissolved in 711 g acetone at 50 ℃, and in 10 minutes, be metered into the solution of 4.8g quadrol in 16g water at 40 ℃ then.Follow-up churning time is 5 minutes.In 15 minutes, disperse by adding 590g water afterwards.By under reduced pressure distilling desolventizing.This obtains having the stable storing polyurethane dispersions of 41.7% solid content and 207nm mean particle size.

Embodiment 12:(invention)

65 ℃ of polycarbonate diol, 22.0 g polyethers LB 25 and 6.7 g neopentyl glycol of introducing 141.2 g Desmophen C, 2200,35.3 g embodiment 2 in advance, and by stirring 5 minutes.In 1 minute, at first add 71.3 g 4 at 65 ℃, two (isocyanato-cyclohexyl) methane (H of 4'- ₁₂MDI) and then add 11.9 g isophorone diisocyanates to this mixture.With mixture heating up to 110 ℃.After 18 hours, reach 3.4% theoretical nco value.Make the prepolymer that makes be dissolved in 600 g acetone at 50 ℃, and in 10 minutes, be metered into the solution of 4.8g quadrol in 16g water at 40 ℃ then.Follow-up churning time is 5 minutes.In 15 minutes, disperse by adding 400g water afterwards.By under reduced pressure distilling desolventizing.This obtains having the stable storing polyurethane dispersions of 41.6% solid content and 219nm mean particle size.

Embodiment 13:Comparative example 11 is with respect to contact angle and 100% modulus of the embodiment of the invention 12

Prepare coating as described in example 10 above like that and carry out contact angle and the measurement of 100% modulus.

Table 2: contact angle and 100% modulus of film that derives from the material of embodiment 12 and 13

The embodiment numbering	Contact angle (°)	100% modulus (N/mm 2)
			Comparative example 11	24	3.3
Embodiment 12	36	9.2

Compare with comparative example 11, the embodiment of the invention 12 comprises polycarbonate diol component of the present invention.Coatingsurface is still very hydrophilic, and 100% modulus rises to almost three times simultaneously.

Embodiment 14:(comparison)

Introduce 282.1 g Desmophen XP, 2613,22.0 g polyethers LB 25 and 6.7 g neopentyl glycol in advance at 65 ℃, and by stirring 5 minutes.In 1 minute, at first add 71.3 g 4 at 65 ℃, two (isocyanato-cyclohexyl) methane (H of 4'- ₁₂MDI) and then add 11.9 g isophorone diisocyanates to this mixture.With mixture heating up to 110 ℃.After 70 minutes, reach 2.5% theoretical nco value.Make the prepolymer that makes be dissolved in 711 g acetone at 50 ℃, and in 10 minutes, be metered into the solution of 4.8g quadrol in 16g water at 40 ℃ then.Follow-up churning time is 5 minutes.In 15 minutes, disperse by adding 590g water afterwards.By under reduced pressure distilling desolventizing.This obtains having the stable storing polyurethane dispersions of 38.3% solid content and 215nm mean particle size.

Embodiment 15:(invention)

65 ℃ of polycarbonate diol, 22.0 g polyethers LB 25 and 6.7 g neopentyl glycol of introducing 141.2 g Desmophen XP, 2613,91.8 g embodiment 1 in advance, and by stirring 5 minutes.In 1 minute, at first add 71.3 g 4 at 65 ℃, two (isocyanato-cyclohexyl) methane (H of 4'- ₁₂MDI) and then add 11.9 g isophorone diisocyanates to this mixture.With mixture heating up to 110 ℃.After 60 minutes, reach theoretical nco value.Make the prepolymer that makes be dissolved in 650 g acetone at 50 ℃, and in 10 minutes, be metered into the solution of 4.8g quadrol in 16g water at 40 ℃ then.Follow-up churning time is 5 minutes.In 15 minutes, disperse by adding 530g water afterwards.By under reduced pressure distilling desolventizing.This obtains having the stable storing polyurethane dispersions of 38.2% solid content and 327nm mean particle size.

Embodiment 16:Comparative example 14 is with respect to contact angle and 100% modulus of the embodiment of the invention 15

Prepare coating as described in example 10 above like that and carry out contact angle and the measurement of 100% modulus.

Table 3: contact angle and 100% modulus of film that derives from the material of embodiment 14 and 15

The embodiment numbering	Contact angle (°)	100% modulus (N/mm 2)
			Comparative example 14	41	3.0
Embodiment 15	41	12.3

Compare with comparative example 14, the embodiment of the invention 15 comprises polycarbonate diol component of the present invention.The contact angle of coating is almost constant, and 100% modulus rises to four times simultaneously.

Embodiment 17:(comparison)

Introduce 269.8 g Desmophen C, 2200,49.7 g polyethers LB 25 and 6.7 g neopentyl glycol in advance at 65 ℃, and by stirring 5 minutes.In 1 minute, at first add 71.3 g 4 at 65 ℃, two (isocyanato-cyclohexyl) methane (H of 4'- ₁₂MDI) and then add 11.9 g isophorone diisocyanates to this mixture.With mixture heating up to 110 ℃.After 21 hours, reach 2.4% theoretical nco value.Make the prepolymer that makes be dissolved in 711 g acetone at 50 ℃, and in 10 minutes, be metered into the solution of 4.8g quadrol in 16g water at 40 ℃ then.Follow-up churning time is 5 minutes.In 15 minutes, disperse by adding 590g water afterwards.By under reduced pressure distilling desolventizing.This obtains having the stable storing polyurethane dispersions of 41.3% solid content and 109nm mean particle size.

Embodiment 18:(invention)

65 ℃ of polycarbonate diol, 49.7 g polyethers LB 25 and 6.7 g neopentyl glycol of introducing 135.0 g Desmophen C, 2200,33.8 g embodiment 2 in advance, and by stirring 5 minutes.In 1 minute, at first add 71.3 g 4 at 65 ℃, two (isocyanato-cyclohexyl) methane (H of 4'- ₁₂MDI) and then add 11.9 g isophorone diisocyanates to this mixture.With mixture heating up to 110 ℃.After 20 hours, reach theoretical nco value.Make the prepolymer that makes be dissolved in 590 g acetone at 50 ℃, and in 10 minutes, be metered into the solution of 4.8g quadrol in 16g water at 40 ℃ then.Follow-up churning time is 5 minutes.In 15 minutes, disperse by adding 590g water afterwards.By under reduced pressure distilling desolventizing.This obtains having the stable storing polyurethane dispersions of 33.7% solid content and 83nm mean particle size.

Embodiment 19:Comparative example 17 is with respect to contact angle and 100% modulus of the embodiment of the invention 18

Prepare coating as described in example 10 above like that and carry out contact angle and the measurement of 100% modulus.

Table 4: contact angle and 100% modulus of film that derives from the material of embodiment 17 and 18

The embodiment numbering	Contact angle (°)	100% modulus (N/mm 2)
			Comparative example 17	11	1.9
Embodiment 18	9	6.0

Compare with comparative example 18, the embodiment of the invention 17 comprises polycarbonate diol component of the present invention.The contact angle of coating is almost constant, and 100% modulus rises to three times simultaneously.

Embodiment 20:(comparison)

Introduce 277.2 g Desmophen C, 2200,33.1 g polyethers LB 25 and 6.7 g neopentyl glycol in advance at 65 ℃, and by stirring 5 minutes.In 1 minute, at first add 71.3 g 4 at 65 ℃, two (isocyanato-cyclohexyl) methane (H of 4'- ₁₂MDI) and then add 11.9 g isophorone diisocyanates to this mixture.With mixture heating up to 110 ℃.After 75 minutes, reach 2.4% theoretical nco value.Make the prepolymer that makes be dissolved in 711 g acetone at 50 ℃, and in 10 minutes, be metered into the solution of 4.8g quadrol in 16g water at 40 ℃ then.Follow-up churning time is 5 minutes.In 15 minutes, disperse by adding 590g water afterwards.By under reduced pressure distilling desolventizing.This obtains having the stable storing polyurethane dispersions of 39.9% solid content and 169nm mean particle size.

Embodiment 21:(invention)

65 ℃ of polycarbonate diol, 33.1 g polyethers LB 25 and 6.7 g neopentyl glycol of introducing 138.6 g Desmophen C, 2200,34.7 g embodiment 2 in advance, and by stirring 5 minutes.In 1 minute, at first add 71.3 g 4 at 65 ℃, two (isocyanato-cyclohexyl) methane (H of 4'- ₁₂MDI) and then add 11.9 g isophorone diisocyanates to this mixture.With mixture heating up to 110 ℃.After 75 minutes, reach theoretical nco value.Make the prepolymer that makes be dissolved in 650 g acetone at 50 ℃, and in 10 minutes, be metered into the solution of 4.8g quadrol in 16g water at 40 ℃ then.Follow-up churning time is 5 minutes.In 15 minutes, disperse by adding 450g water afterwards.By under reduced pressure distilling desolventizing.This obtains having the stable storing polyurethane dispersions of 40.0% solid content and 167nm mean particle size.

Embodiment 22:Comparative example 20 is with respect to contact angle and 100% modulus of the embodiment of the invention 21

Prepare coating as described in example 10 above like that and carry out contact angle and the measurement of 100% modulus.

Table 5: contact angle and 100% modulus of film that derives from the material of embodiment 20 and 21

The embodiment numbering	Contact angle (°)	100% modulus (N/mm 2)
			Comparative example 20	14	1.6
Embodiment 21	16	6.1

Compare with comparative example 20, the embodiment of the invention 21 comprises polycarbonate diol component of the present invention.The contact angle of coating is almost constant, and 100% modulus rises to almost four times simultaneously.

Claims (13)

1. the polyurethane-urea dispersion that comprises polyurethane-urea, this polyurethane-urea

(1) by at least one based on the copolymer unit end-blocking of polyethylene oxide and poly(propylene oxide) and

(2) comprise the unit based on polycarbonate polyol of formula (I)

Formula (I).

2. according to the polyurethane-urea dispersion of claim 1, be characterised in that the polyurethane-urea that wherein exists does not contain ion or ionogenic group.

3. according to the polyurethane-urea dispersion of claim 1 or 2, be characterised in that the polyurethane-urea that wherein exists based on the polycarbonate polyol component, this component has the average hydroxy functionality of 1.7-2.3.

4. according to the polyurethane-urea dispersion of claim 3, be characterised in that the polycarbonate polyol component has the polycarbonate polyol a1 that obtains by the two functional alcohol reaction that makes carbonic acid derivatives and formula (II))

Formula (II).

5. according to the polyurethane-urea dispersion of claim 4, be characterised in that the polycarbonate polyol component is except polycarbonate polyol a1) also have other polycarbonate polyol a2).

6. according to the polyurethane-urea dispersion of claim 5, be characterised in that described polycarbonate polyol a2) be based on 1,6-hexylene glycol, 1, the compound of the average hydroxy functionality with 1.7-2.3 of 4-butyleneglycol or its mixture and the 400-6000g/mol molecular weight measured by the OH value.

7. according to the polyurethane-urea dispersion of claim 1 or 2, be characterised in that, total share by epoxy alkane unit, be used for the copolymer unit of the polyethylene oxide of end-blocking and poly(propylene oxide) based on deriving from 40mol% ethylene oxide unit and the mixing polyalkylene oxide polyethers of the monohydroxy official energy of 60mol% propylene oxide units at least at the most, this mixing polyalkylene oxide polyethers has the 500g/mol-5000g/mol number-average molecular weight.

8. according to the polyurethane-urea dispersion of claim 1 or 2, be characterised in that in N,N-DIMETHYLACETAMIDE 30 ℃ of measurements, wherein the polyurethane-urea of Cun Zaiing has the number-average molecular weight of 5000-100000g/mol.

9. according to the polyurethane-urea dispersion of claim 1 or 2, be characterised in that this polyurethane-urea dispersion comprises pharmacological active substance.

10. preparation is according to each the method for polyurethane-urea dispersion of claim 1-9, wherein make the polycarbonate polyol component a), at least a polyisocyanate component b), at least a polyoxy alkylidene ether amount of component b), at least a diamine and/or amino alcohol components d) and optional other polyol component react each other, and in water, disperse.

11. can be by the polyurethane-urea that obtains according to each polyurethane-urea dispersion of claim 1-9.

12. the coating that can use the polyurethane-urea according to claim 11 to obtain.

13. use the base material according to the coating coating of claim 12.